Disperse azo dye mixtures

ABSTRACT

The present invention relates to dye mixtures comprising at least one compound of the formula (I) 
                         
and at least one compound of the formula (II)
 
                         
where the substituents are each as defined in the description part, which are highly useful for dyeing and printing hydrophobic synthetic material.

The invention relates to disperse azo dye mixtures, processes for theirpreparation and to their use for dyeing and printing hydrophobicsynthetic materials.

It is an object of the present invention to provide navy to blackdisperse dye mixtures having good application properties.

The invention accordingly provides a dye mixture comprising at least onedye of the formula (I)

where

-   -   R¹ is hydrogen, C₁-C₄alkyl, halogen, especially Cl and Br, or        C₁-C₄-alkoxy,    -   n is 1 or 2, and the    -   ring A is optionally substituted, possible substituents being        one or more identical or different substituents, preferably        C₁-C₄-alkyl, especially CH₃, and also halogen, especially Cl and        Br,    -   and at least one dye of the formula (II)

where

-   -   X is halogen, especially Cl and Br, or CN,    -   R² and R⁵ are independently hydrogen or C₁-C₄-alkyl, and    -   R³ and R⁴ are independently hydrogen, optionally substituted        C₁-C₄-alkyl or C₂-C₄-alkenyl,    -   possible substituents for alkyl being preferably selected from        —OH, —CN, —OCOR, —OCOC₆H₅, —OCOOR, —COOR, —OC₆H₅, —C₆H₅ and/or        C₁-C₄-alkoxy, R being hydrogen or C₁-C₄-alkyl.

Dyes of the formula (I) are known for example from CN-A-1 036 974 (=CA114: 145 436) and dyes of the formula (II) for example from DE-A-2 818653.

Preferred mixtures contain compounds of the formula (I) where the ring Adoes not bear any further substituents. Particular preference is givento compounds of the formula (I) where R¹ is hydrogen or C₁-C₄-alkyl,especially methyl. Very particular preference is given to mixtures ofthe invention which comprise the dye of the formula (I) where n is 1, R¹is hydrogen or methyl, and the ring A is not further substituted.

Preferred mixtures contain a dye of the formula (II) where X is halogen,especially Cl or Br. Particularly preferred dyes of the formula (II) arethose

where

-   -   R³ and R⁴ are independently hydrogen, C₂-C₄-alkenyl,        unsubstituted C₁-C₄-alkyl or ROCO—, NC— or ROOC-substituted        C₁-C₄-alkyl, R being as defined above.

In particular, in the formula (II), R² and R⁵ are independentlyC₁-C₄-alkyl, preferably CH₃.

Particularly preferred mixtures according to the invention are thosewhich contain at least one dye of the formula (I) selected from thegroup:

and at least one dye of the formula (II) selected from the group:

Preference is further given to mixtures of the invention whichadditionally contain a further dye of the formula (III), (IV) and/or (V)

where

-   -   X¹ is halogen, especially Cl and Br, or CN,    -   X² is halogen, especially Cl and Br, hydrogen, NO₂ or CN,    -   R⁶ is C₁-C₄-alkyl,    -   R⁷ and R⁸ are independently hydrogen, unsubstituted or HO—, NC—,        ROCO—, H₅C₆OCO—, (C₁-C₄-alkyl) OOCO—, ROOC—, H₅C₆O—, H₅C₆-        and/or C₁-C₄-alkoxy-substituted C₁-C₄-alkyl or C₂-C₄-alkenyl, R        being as defined above,    -   Y¹ and Y² are independently hydrogen or halogen, especially Cl        and Br,    -   R⁹ and R¹⁰ are independently hydrogen, unsubstituted or HO—,        NC—, ROCO—, H₅C₆OCO— and/or C₁-C₄-alkoxy-substituted        C₁-C₄-alkyl, R being as defined above, or C₂-C₄-alkenyl,    -   R¹¹ is C₁-C₄-alkyl, and    -   R¹² is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy.

Particularly preferred mixtures are those which, as well as the dyes ofthe formulae (I) and (II), contain a dye of the formula (III), inparticular dyes of the formula (III) selected from the group (IIIa) and(IIIb):

Likewise particularly preferred mixtures are those which, as well as thedyes of the formulae (I) and (II), contain a dye of the formula (IV), inparticular dyes of the formula (IV) selected from the group (IVa), (IVb)and (IVc)

Particularly preferred mixtures further includes those which, as well asthe dyes of the formulae (I) and (II), contain a dye of the formula (V),especially the dye of the formula (Va)

The dye mixture of the invention preferably comprises 1 to 99%,preferably 1 to 80%, especially 5 to 60%, by weight of at least one dyeof the formula (I) and 1 to 99%, preferably 20 to 99%, especially 40 to95%, by weight of at least one dye of the formula (II), based on thetotal amount of dye.

Preference is given to using the dye of the formula (III) in an amountof 0 to 80%, especially 2 to 60%, by weight, based on the total amountof dye.

Preference is given to using the dye of the formula (IV) in an amount of0 to 40%, especially 5 to 30% by weight, based on the total amount ofdye.

Preference is given to using the dye of the formula (V) in an amount of0 to 40%, especially 5 to 30% by weight, based on the total amount ofdye.

The dye mixtures of the invention lead to black to navy shades,especially with the above-specified mixing ratios.

The mixtures of the invention are especially notable for excellentsublimation fastness and good affinity. Also, the colour yield isconsistently high over a wide pH range. They are especially useful foralkaline polyester dyeing, especially at a pH of 8 to 11.

The dye mixture of the invention may include further disperse dyes.

The invention further relates to a process for producing the dye mixtureof the invention, characterized in that the individual dyes (I) and (II)and optionally further dyes of the dye mixture are ground in water inthe presence of a dispersant, then mixed and optionally dried or in thatthe dyes (I), (II) and optionally further ones are mixed, ground inwater in the presence of a dispersant and optionally dried.

Novel dye mixtures of the dyes of the formulae (I), (II) and optionallyone or more dyes of the general formulae (III) to (V) can be preparedfor example by simply mixing the components. The mixing can beaccomplished by mixing separately finished individual components in thedyeing liquor or else, preferably, by mixing the press cakes of theindividual components and conjointly finishing the mixture.

The finish is characterized in that the dyes are ground in the presenceof a dispersant to convert them into an aqueous dispersion, i.e. into aliquid or, after drying, into a pulverulent dye preparation, for whichthe individual dyes can first be separately finished and then mixed orthe individual dyes can first be mixed and then conjointly finished.This grinding preferably takes place in mills, for example ball,vibratory, bead or sand mills, or in kneaders. After grinding, the dyeparticle size is preferably about 0.1 to 10 μm, especially about 1 μm.The grinding preferably takes place in the presence of dispersants,which can be nonionic or anionic. Nonionic dispersants are for examplereaction products of alkylene oxides, for example ethylene oxide orpropylene oxide, with alkylatable compounds, for example fatty alcohols,fatty amines, fatty acids, phenols, alkylphenols and carboxamides.Anionic dispersants are for example ligninsulphonates and salts thereof,alkyl- or alkylarylsulphonates, alkylaryl polyglycol ether sulphates,alkali metal salts of the condensation products of naphthalenesulphonicacids and formaldehyde, polyvinyl sulphonates and ethoxylated novolaks.

The invention therefore also provides dye preparations comprising

-   -   10 to 60% by weight of the dye mixture of the invention, and    -   40 to 90% by weight of the dispersant.

The dye preparations can be present in liquid or solid form, in whichcase the liquid preparations are preferably aqueous dye dispersions andthe solid preparations are present as powder or granules.

Preferred aqueous dye preparations comprise water,

-   -   15 to 50% by weight of the dye mixture of the invention, and    -   10 to 25% by weight of dispersant, each based on the dye        preparation.

Preferred dispersants are the abovementioned nonionic and anionicdispersants.

The dye preparations of the invention may comprise further auxiliaries,for example auxiliaries which act as oxidizing agents, e.g. sodiumm-nitrobenzenesulphonate, or fungicidal agents, e.g. sodiumo-phenylphenoxide and sodium pentachlorophenoxide. It is also possiblefor wetting agents, antifreeze agents, dustproofing agents orhydrophilicizing agents to be included.

For certain applications, solid preparations such as powder or granulepreparations are preferred. Preferred solid dye preparations comprise

-   -   30 to 50% by weight of the dye mixture of the invention, and    -   70 to 50% by weight of the dispersant.

They may optionally further comprise auxiliaries, for example wetting,oxidizing, preserving and dustproofing agents.

A preferred process for producing the solid preparations consists indepriving the above-described liquid dye preparations of their liquid,for example by vacuum drying, freeze drying, by drying on drum dryers,but preferably by spray drying.

Dye mixtures of the invention, however, can preferably also be producedby conjoint finishing of the mixing components.

To this end, the mixing components are dispersed in a suitable mixingratio as described above by a grinding operation in water and optionallyconverted into a solid dye preparation by removing the water.

To improve the properties of the dye preparations, it can beadvantageous to subject the mixing components to a heat treatment priorto grinding. The heat treatment takes place at 25 to 98° C., preferablyat 30 to 80° C., particularly preferably at 40 to 60° C. It isadvantageous to carry out the finishing, i.e. the conversion into thecommercially customary solid or liquid preparations, immediately afterthe heat treatment, without intermediary isolation. For this purpose,the heat-treated suspension is converted into a dispersion by grinding.It is advantageous in this connection to carry out the heat treatment inthe presence of those dispersants and optionally also auxiliaries whichare to be included in the finished solid or liquid preparation. Theseare identical with the abovementioned surface-active substances. If thetotal amount of these dispersants and auxiliaries was not added duringthe heat treatment, the remainder will be added prior to grinding. Inthis case, generally 10 to 400% by weight, preferably 20 to 200% byweight, of surface-active substances, based on the dye mixtures, areadded for the heat treatment.

To produce dyeing liquors, the requisite amounts of the dye preparationsproduced in accordance with the above directions are diluted with thedyeing medium, preferably water, to such an extent that a liquor ratioof 5:1 to 50:1 is obtained for the dyeing. In addition, the liquorsgenerally have added to them further dyeing auxiliaries, such ascarriers, dispersants and wetting agents.

If the dye mixture of the invention is to be used for textile printing,then the requisite amounts of the dye preparation are kneaded,preferably together with thickeners, for example alkali metal alginatesor the like, optionally further additives, for example fixationaccelerants, wetting agents and hydration agents, to form print pastes.

The dye mixtures of the invention, which incidentally may includefurther dyes, are very useful for dyeing and printing hydrophobicsynthetic materials. Examples of suitable hydrophobic syntheticmaterials are cellulose acetate, cellulose triacetate, polyamides andhigh molecular weight polyesters. The dye mixtures of the invention arepreferably used for dyeing and printing materials composed of highmolecular weight polyesters, especially those based on polyethyleneglycol terephthalates, or their mixtures with natural fibre materials,especially wool or cellulose, or for dyeing and printing materialscomposed of cellulose triacetate.

The hydrophobic synthetic materials can be present in the form ofsheetlike or filamentary structures and may have been processed forexample into yarns or woven or knitted textile materials. The dyeing ofthe fibre material mentioned with the dye mixtures of the invention canbe carried out in a conventional manner, preferably from aqueousdispersion, optionally in the presence of carriers, between 80 to about110° C. by the exhaust method or by the HT method in a dyeing autoclaveat 110 to 140° C., and also by the so-called thermofix method, wherebythe fabric is padded with the dyeing liquor and then set/fixed at about180 to 230° C. The printing of the materials mentioned can be carriedout in a conventional manner by incorporating the dye mixtures of theinvention into a print paste and treating the fabric printed therewithat temperatures between 180 to 230° C. with HT steam or dry heat to fixthe dyes, optionally in the presence of a carrier. This produces verystrong olive, navy or black dyeings and prints having very goodfastnesses, especially having very good light, rub, dry heat setting andpleating, washing, water and sublimation fastness properties.

The dye mixtures of the invention exhibit excellent wettingcharacteristics when used for making up dyeing and padding liquors andalso print pastes and are rapidly dispersible without extensive manualor mechanical stirring. The liquors and print pastes are homogeneous andgive trouble-free processing in modern dyehouse drugstores withoutblocking the nozzles.

The liquid preparations of the invention do not separate and, inparticular, do not form a sticky sediment. There is thus no need for anyextensive homogenization of the dye in its container before the dye isremoved.

The millbase produced on grinding the dyes in the presence ofdispersants and auxiliaries to produce solid preparations is stable fora prolonged period, even at elevated temperature. The millbase need notbe cooled in the mills or after leaving the mills and can be kept for aprolonged period in collection vessels prior to spray drying.

The thermal stability of the dye mixture of the invention also showsitself in the fact that spray drying can be carried out at hightemperatures without agglomeration of the material to be dried. For thesame dryer outlet temperature, a higher inlet temperature means betterdryer performance and thus reduced manufacturing costs.

The above-described dye preparations are very useful for making up printpastes and dyeing liquors. They offer particular advantages for examplein relation to continuous processes, where the dye concentration of thedyeing liquors has to be kept constant by continuously feeding dye intothe running apparatus.

The advantage of the dye mixtures of the invention becomes particularlyclear when dyeing from an aqueous dyebath under modern industrialconditions.

The modern industrial conditions mentioned are characterized by highpack densities in the case of package and beam dyeings, short liquorratios, i.e. high dye concentrations, and also high shearing forces inthe dyeing liquor due to high pumping rates. The dye mixtures of theinvention do not agglomerate even under these conditions, nor filter outon the textile materials to be dyed. Thus, homogeneous dyeings areobtained without colour strength differences between the outer and innerlayers of the wound packages, and the dyeings do not shed any dyedeposits. Pad dyeings and prints with the dye mixture of the inventionproduce a material of homogeneous, speckle-free appearance.

The dye mixtures of the invention are also useful for dyeing theabove-cited hydrophobic materials from organic solvents by the methodsknown for this purpose and for mass coloration.

The invention therefore also provides for the use of the dye mixtures ofthe invention for dyeing and printing hydrophobic synthetic materials,especially fibre materials, and for the mass coloration of hydrophobicsynthetic materials.

The examples hereinbelow illustrate the invention.

EXAMPLES Example 1

-   -   a) 13.3 g of the dye of the formula (1)

-   -   and    -    11 g of the dye of the formula (2)

-   -   and also    -    13.7 g of the dye of the formula (3)

-   -   and    -    6.0 g of the dye of the formula (4)

-   -    were ground together with 300 ml of water and 56 g of a        ligninsulphonate (sodium salt) in a bead or sand mill for 3        hours and then spray dried (inlet temperature 130° C., outlet        temperature 60° C.). The resulting powder (about 100 g) is        readily dispersible in water.    -   b) 0.4 g of the above-prepared powder were treated together with        10 g of polyester textile material at pH 4.5 and 130° C. by a        normal HT dyeing process for about 60 min. Washing, rinsing and        drying left a jet black dyeing having very good fastness        properties.

The method of Example 1 was followed to produce further dye mixtures andused them for polyester dyeing by using 13.3 g of the dye 1 of Example 1and 11 g of the dye of the general formula (II) where the substituentsare each as defined in Table 1.

TABLE 1 dye of formula (II) used Ex. X R² R⁵ R³ R⁴ 2 Cl C₂H₅ C₂H₅CH₂CH₂CN CH₂CH₂COOCH₃ 3 Br CH₃ CH₃ CH₂CH₂—OCH₃ CH₂CH₂—OCH₃ 4 Br CH₃ C₂H₅CH₂CH₂—OCOC₆H₅ CH₂CH₂—OCOC₆H₅ 5 Br CH₃ CH₃ CH₂CH₂—OCOCH₃ CH₂CH₂—OCOCH₃ 6Br CH₃ CH₃ CH₂CH₂CN CH₂—C₆H₅ 7 Cl CH₃ C₂H₅ CH₂CH₂CN H 8 Br CH₃ CH₃CH₂CH₂COOCH₃ CH₂CH₂COOCH₃

Example 9

The method of Example 1 was followed to grind

-   -   5 g of the dye of the formula (6)

-   -   and    -    39 g of the dye of the formula (5)

-   -    and dry the millbase. The ligninsulphonate (sodium salt) was        used in the same ratio to the total amount of dye as in        Example 1. The dye mixture obtained (0.1 g) was then used for        dyeing 10 g of polyester fibres to obtain bright navy dyeings        having good wash and sublimation fastness properties.

The method of Example 9 was repeated to combine the following dyes ofthe formulae I and II as per Table 2. The I:II weight ratio of Example 9was maintained. Greenish to reddish navy dyeings were obtained.

TABLE 2 Dye of formula Ex. (I)* Dye of formula (II) No. R¹ X R² R⁵ R³ R⁴10 H Cl CH₃ CH₃ CH₂—CH₂OCOCH₃ CH₂CH₂OCOCH₃ 11 CH₃ Cl C₂H₅ CH₃CH₂CH₂OCOCH₃ CH₂CH₂OCOCH₃ 12 Cl Br C₂H₅ CH₃ CH₂CH₂OCOCH₃ CH₂CH₂OCOCH₃ 13H Cl CH₃ CH₃ C₂H₅ C₂H₅ 14 H Br CH₃ CH₃ C₂H₅ C₂H₅ 15 H Cl CH₃ CH₃CH₂—CH═CH₂ CH₂—CH═CH₂ 16 H Br CH₃ CH₃ CH₂—CH═CH₂ CH₂—CH═CH₂ 17 CH₃ BrCH₃ CH₃ CH₂—CH═CH₂ H 18 CH₃ Cl CH₃ CH₃ CH₂—CH═CH₂ H 19 H Br C₂H₅ CH₃C₂H₅ C₂H₅ 20 H Cl C₂H₅ CH₃ C₂H₅ C₂H₅ 21 CH₃ Cl CH₃ CH₃ CH₂CH₂OCOC₂H₅CH₂CH₂OCOC₂H₅ 22 H Br CH₃ CH₃ CH₂CH₂OCOC₂H₅ CH₂CH₂OCOC₂H₅ *The ring Adoes not bear any further substituents; n = 1

Example 23

24 g of the dye of the formula (6) from Example 9 and 7 g of the dye ofthe formula (3) from Example 1 and also 22 g of the dye of the formula(5)

were ground together with 300 g of water and 53 g of sodiumligninsulphonate, and dried, similarly to Example 1.

When 0.35 g of this dye mixture is used for dyeing polyester fabricsimilarly to Example 1b, reddishly bloomy black dyeings are obtained.

When dye (5) of Example 23 was replaced by the same amount of a dye ofthe formula (II) as per Table 3 below, further reddish black dyeingshaving good fastness properties were obtained on polyester.

TABLE 3 Substituent meanings for the dye of the formula (II) Ex. No. XR² R⁵ R³ R⁴ 24 Cl CH₃ CH₃ C₂H₄OCOCH₃ C₂H₄OCOCH₃ 25 Br C₂H₅ CH₃C₂H₄OCOCH₃ C₂H₄OCOCH₃ 26 Cl C₂H₅ CH₃ C₂H₄OCOCH₃ C₂H₄OCOCH₃ 27 Br CH₃C₂H₅ C₂H₄OCOCH₃ C₂H₄OCOCH₃ 28 Cl CH₃ C₂H₅ C₂H₄OCOCH₃ C₂H₄OCOCH₃ 29 BrCH₃ CH₃ C₂H₄OCOC₂H₅ C₂H₄OCOC₂H₅ 30 Cl CH₃ CH₃ C₂H₄OCOC₂H₅ C₂H₄OCOC₂H₅ 31Cl CH₃ CH₃ C₂H₄COOCH₃ C₂H₄COOCH₃ 32 Br CH₃ CH₃ C₂H₄CN C₂H₄CN 33 Br CH₃CH₃ C₂H₄OCH₃ C₂H₄OCH₃ 34 Cl CH₃ CH₃ C₂H₄CN CH₂C₆H₅

Example 35

17.6 g of the dye of the formula (6) from Example 9, 9.4 g of the dye ofthe formula (2) from Example 1 and 11.0 g of dye (3) from Example 1 wereground together with 62 g of sodium ligninsulphonate and 300 g of water,and dried, similarly to Example 1.

0.6 g of the resulting powder was dyed together with 10 g of polyesterfabric at pH 8.5 to 9 by means of a glycine/NaOH buffer at 130° C. for60 min. A deep black textile material is obtained.

On replacing the dye of the formula (2) in Example 35 with the sameamount of a dye of formula (II) of Table 4 below and using thesemixtures to dye polyester similarly to Example 35, deep black dyeingswere again obtained.

TABLE 4 Dye components of the formula (II) used Ex. No. X R² R⁵ R³ R⁴ 36Cl CH₃ CH₃ C₂H₅ C₂H₅ 37 Br C₂H₅ CH₃ C₂H₅ C₂H₅ 38 Cl C₂H₅ CH₃ C₂H₅ C₂H₅39 Cl CH₃ CH₃ CH₂—CH═CH₂ CH₂—CH═CH₂ 40 Br CH₃ CH₃ CH₂—CH═CH₂ CH₂—CH═CH₂41 Cl CH₃ CH₃ CH₂—CH═CH₂ H 42 Br CH₃ CH₃ CH₂—CH═CH₂ H 43 Cl C₂H₅ CH₃CH₂—CH═CH₂ CH₂—CH═CH₂ 44 Br C₂H₅ CH₃ CH₂—CH═CH₂ CH₂—CH═CH₂ 45 Cl CH₃C₂H₅ CH₂—CH═CH₂ CH₂—CH═CH₂ 46 Br CH₃ C₂H₅ CH₂—CH═CH₂ CH₂—CH═CH₂ 47 ClCH₃ C₂H₅ C₂H₅ C₂H₅ 48 Br CH₃ C₂H₅ C₂H₅ C₂H₅

Example 49

The method of Example 1 was followed to dye polyester fabric with a dyemixture comprising

-   -   16.7 g of the dye of the formula (6) from Example 9,    -   6.1 g of the dye of the formula (7)

-   -   11.9 g of the dye of the formula (8)

-   -   and    -    15.3 g of the dye of the formula (9)

This mixture was bead milled in the presence of 50 g of sodiumligninsulphonate and 650 g of water and then spray dried.

0.1 g of this mixture was used for dyeing 5 g of polyester fabric. Blackdyeings were obtained.

Examples 49 to 53

The method of Example 48 was followed to dye the mixtures of Table 5below. In all cases, good pH dependence, excellent bath exhaustion andgood sublimation fastness properties were obtained as results.

TABLE 5 Dye I* Ex. R Dye (7) Dye II Dye III No. n 1 from Ex. 49 X R²R³═R⁴ R⁵ X¹ X² R⁷═R⁸ R⁶ 49 1 H from Ex. 49 Cl CH₃ CH₂CH═CH₂ CH₃ Cl NO₂C₂H₅ CH₃ 50 1 H from Ex. 49 Cl C₂H₅ C₂H₅ C₂H₅ Cl NO₂ C₂H₅ CH₃ 51 1 Hfrom Ex. 49 Br CH₃ C₂H₅ CH₃ Br NO₂ C₂H₅ CH₃ 52 1 H from Ex. 49 Cl CH₃C₂H₅ CH₃ Br NO₂ C₂H₅ CH₃ 53 1 H from Ex. 49 Br CH₃ CH₂CH═CH₂ CH₃ Br NO₂C₂H₅ CH₃ *Ring A not further substituted

What is claimed is:
 1. A mixture comprising 5 to 60% by weight of atleast one compound of the formula (I)

where R¹ is hydrogen, C₁-C₄-alkyl, halogen, or C₁-C₄-alkoxy, n is 1 or2, and the ring A is optionally substituted unsubstituted, and 20 to 95%by weight of at least one compound of the formula (II)

where X is halogen, or CN, R² and R⁵ are independently hydrogen orC₁-C₄-alkyl, and R³ and R⁴ are independently hydrogen, optionallysubstituted C₁-C₄-alkyl or C₂-C₄-alkenyl or unsubstituted C₁-C₄-alkyl,based on total amount of dye in the mixture.
 2. The mixture of claim 1,comprising at least one compound of the formula (I) where the ring Adoes not bear any further substituents.
 3. The mixture of claim 1,comprising at least one compound of the formula (I) where R¹ is hydrogenor C₁-C₄-alkyl.
 4. The mixture of claim 1, comprising at least onecompound of the formula (I), where n is 1, R¹ is hydrogen or methyl andthe ring A is not further substituted.
 5. The mixture of claim 1,comprising compounds of the formula (II) where X is halogen.
 6. Themixture of claim 1, comprising compounds of the formula (II) where R³and R⁴ are independently hydrogen, C₂-C₄-alkenyl, unsubstitutedC₁-C₄-alkyl or ROCO—, NC— and/or ROOC-substituted C₁-C₄-alkyl, R beinghydrogen or C₁-C₄-alkyl.
 7. The mixture of claim 1, further comprising acompound of the formula (III), (IV) and/or (V)

where X¹ is halogen or CN, X² is halogen, hydrogen, NO₂ or CN, R⁶ isC₁-C₄-alkyl, R⁷ and R⁸ are independently hydrogen, unsubstituted or HO—,NC—, ROCO—, H₅C₆OCO—, (C₁-C₄-alkyl) OOCO—, ROOC—, H₅C₆O—, H₅C₆— and/orC₁-C₄-alkoxy-substituted C₁-C₄-alkyl and/or C₂-C₄-alkenyl, R beinghydrogen or C₁-C₄-alkyl, Y¹ and Y² are independently hydrogen orhalogen, R⁹ and R¹⁰ are independently hydrogen, unsubstituted or HO—,NC—, ROCO—, H₅C₆OCO— and/or C₁-C₄-alkoxy-substituted C₁-C₄-alkyl, Rbeing as defined above, or C₂-C₄-alkenyl, R¹¹ is C₁-C₄-alkyl, and R¹² ishydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy.
 8. The mixtures of claim 1,comprising 1 to 99% by weight, especially 1 to 80% by weight, of atleast one compound of the formula (I) and 1 to 99% by weight, especially20 to 99% by weight, of at least one compound of the formula (II), basedon total amount of dye.
 9. A dye preparation comprising 10 to 60% byweight of dye mixture according to claim 1, and 40 to 90% by weight ofdispersant.
 10. A process for producing the dye preparation of claim 8claim 9, in which the individual dyes of the dye mixture of claim 1 areground in water in the presence of a dispersant, then mixed andoptionally dried or in which the dye mixture of claim 1 is ground inwater in the presence of a dispersant and optionally dried.
 11. A methodfor dyeing and printing hydrophobic synthetic materials or for masscoloration of hydrophobic synthetic materials in which the dye mixtureof claim 1 is used.
 12. The A hydrophobic synthetic material dyed orprinted with the dye mixture of claim
 1. 13. The mixture of claim 1,further comprising 2 to 60% by weight of at least one compound of theformula (III), based on the total amount of dye in the mixture,

X¹ is halogen, X² is halogen, hydrogen, NO₂ or CN, R⁶, R⁷ and R⁸ areindependently C₁-C₄-alkyl.
 14. A process for producing the dyepreparation of claim 9, in which the individual dyes of the dye mixtureare ground in water in the presence of a dispersant, then mixed andoptionally dried or in which the dye mixture is ground in water in thepresence of a dispersant and optionally dried wherein the mixturecomprises 5 to 60% by weight of at least one compound of the formula (I)and 20 to 95% by weight of at least one compound of the formula (II),based on total amount of dye.